EP4139420A1 - Économie circulaire de déchets plastiques en polypropylène par raffinage d'huile avec filtration et traitement d'oxyde métallique d'huile de pyrolyse - Google Patents

Économie circulaire de déchets plastiques en polypropylène par raffinage d'huile avec filtration et traitement d'oxyde métallique d'huile de pyrolyse

Info

Publication number
EP4139420A1
EP4139420A1 EP21793603.8A EP21793603A EP4139420A1 EP 4139420 A1 EP4139420 A1 EP 4139420A1 EP 21793603 A EP21793603 A EP 21793603A EP 4139420 A1 EP4139420 A1 EP 4139420A1
Authority
EP
European Patent Office
Prior art keywords
pyrolysis
metal oxide
refinery
pyrolysis oil
oxide treatment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21793603.8A
Other languages
German (de)
English (en)
Other versions
EP4139420A4 (fr
Inventor
Hye-Kyung Timken
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chevron USA Inc
Original Assignee
Chevron USA Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chevron USA Inc filed Critical Chevron USA Inc
Publication of EP4139420A1 publication Critical patent/EP4139420A1/fr
Publication of EP4139420A4 publication Critical patent/EP4139420A4/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/12—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by dry-heat treatment only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/06—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by heating, cooling, or pressure treatment
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/09—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by filtration
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/24—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with hydrogen-generating compounds
    • C10G45/26—Steam or water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
    • C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
    • C10G55/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one catalytic cracking step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • U.S. Pat. No. 3,845,157 discloses cracking of waste or virgin polyolefins to form gaseous products such as ethylene/olefm copolymers which are further processed to produce synthetic hydrocarbon lubricants.
  • U.S. Pat. No. 4,642,401 discloses the production of liquid hydrocarbons by heating pulverized polyolefin waste at temperatures of 150-500° C. and pressures of 20-300 bars (2-30 MPa).
  • U.S. Pat. No. 5,849,964 discloses a process in which waste plastic materials are depolymerized into a volatile phase and a liquid phase.
  • the volatile phase is separated into a gaseous phase and a condensate.
  • the liquid phase, the condensate and the gaseous phase are refined into liquid fuel components using standard refining techniques.
  • U.S. Pat. No. 6,143,940 discloses a procedure for converting waste plastics into heavy wax compositions.
  • U.S. Pat. No. 6,150,577 discloses a process of converting waste plastics into lubricating oils.
  • EP0620264 discloses a process for producing lubricating oils from waste or virgin polyolefins by thermally cracking the waste in a fluidized bed to form a waxy product, optionally using a hydrotreatment, then catalytically isomerizing and fractionating to recover a lubricating oil.
  • Other documents which relate to processes for converting waste plastic into lubricating oils include U.S. Patent Nos. 6,288,296; 6,774,272; 6,822,126; 7,834,226; 8,088,961;
  • a continuous process for converting waste plastic into recycle for polypropylene polymerization comprises selecting waste plastics containing polyethylene and/or polypropylene. These waste plastics are then passed through a pyrolysis reactor to thermally crack at least a portion of the polyolefin waste and produce a pyrolyzed effluent. The pyrolyzed effluent is separated into offgas, a pyrolysis oil comprising naphtha, diesel and heavy fractions, and char. Pyrolysis wax can also be produced in addition to the pyrolysis oil.
  • the incorporation of the process with an oil refinery is an important aspect of the present process, and allows the creation of a circular economy with a single use waste plastic such as polyethylene or polypropylene.
  • the pyrolysis oil for example, the entire liquid fraction from the pyrolysis unit, is passed to a refinery FCC unit from which can be recovered liquid petroleum olefin streams.
  • a C3 olefin stream from the FCC unit can be isolated and passed to a propylene polymerization unit.
  • Another important aspect of the present process is the upgrading of the liquid pyrolysis product before the stream is integrated with a refinery unit.
  • the pyrolysis oil and wax waste plastics contain contaminants that cannot be fed in a large quantity to refinery units, such as an FCC unit, as they deactivate the refining catalysts, cause plugging in the unit or cause corrosion in processing units, which are commonly made of carbon steel.
  • refinery units such as an FCC unit
  • the use of fine filtration followed by a metal oxide treatment has been found to be an effective treatment process to upgrade the pyrolysis products for then safely processing in refinery units.
  • the use of the fine filtration and metal oxide treatment allows effective recycling in large volumes when integrated with a refinery.
  • a continuous process for converting waste plastic comprising polyethylene and polypropylene into recycle for polypropylene polymerization is provided.
  • the process comprises selecting waste plastics containing polyethylene and/or polypropylene and then passing the waste plastics through a pyrolysis reactor to thermally crack at least a portion of the polyolefin waste and produce a pyrolyzed effluent.
  • the pyrolyzed effluent is separated into offgas, a pyrolysis oil comprising naphtha, diesel and heavy fractions, and char.
  • the pyrolysis oil, the entire liquid fraction from the pyrolysis unit is subjected to a fine filtration and then a metal oxide treatment.
  • the resulting treated pyrolysis product is then safely passed to a refinery FCC unit.
  • the FCC unit will convert the treated pyrolysis oil product into FCC hydrocarbon product.
  • the FCC product is sent to a FCC unit separation section to produce offgas, C3, C4, FCC gasoline and heavy fractions.
  • C4 is separated from the mixture to leave a C3 olefin/paraffm mixture, which mixture is separated into C3 paraffin and C3 olefin fractions.
  • the C3 olefin is passed to a propylene polymerization reactor.
  • the C3 paraffin is passed to a dehydrogenation unit to produce propylene for subsequent polymerization to polypropylene.
  • the FCC gasoline recovered is sent to a gasoline blending pool.
  • the heavy portion of the hydrocarbon from the FCC unit distillation is sent to appropriate refinery units for upgrading into clean gasoline and diesel.
  • the C4 LPG fraction recovered contains butanes and butenes and can also be sent to various upgrading processes to make clean gasoline and diesel.
  • the treated pyrolysis oil is passed to a refinery FCC Feed Pretreater Unit prior to the FCC unit.
  • This unit is effective in removing sulfur, nitrogen, phosphorus, silica, dienes and metals that will hurt a FCC unit catalyst performance. Also this unit hydrogenates aromatics and improves the liquid yield of the FCC unit.
  • refinery operations it has been found that by adding refinery operations one can upgrade the waste pyrolysis oil (and wax) to higher value products such as gasoline, diesel, and base oil. Also, by adding refinery operations it has been found that clean naphtha (CVCx) or C4 or C3 can be efficiently and effectively produced from the waste pyrolysis oil for ultimate polypropylene polymer production.
  • FIG. 1 depicts the current practice of pyrolyzing waste plastics to produce fuel or wax (base case).
  • FIG. 2 depicts a present process for filtration/metal oxide treatment of pyrolysis oil at the pyrolysis facility.
  • FIG. 3 depicts a present process for establishing a circular economy for waste plastics to recycled polypropylene in accordance with the present processes including filtration/metal oxide treatment of pyrolysis oil occurring in a refinery.
  • FIG. 4 depicts the plastic type classification for waste plastics recycling.
  • Polypropylene is the second-most widely produced commodity plastic after polyethylene, with about 60 million ton per year being globally produced. It is used widely in various consumer and industrial products such as in packaging (rugged reusable containers and bottles, clear bags or clear containers), labeling, pipe, fibers, foams, clothing etc.
  • Polypropylene has properties similar to polyethylene, but it is slightly harder and more heat resistant, and has higher chemical resistance.
  • the industrial manufacturing processes can be grouped into gas phase polymerization, bulk polymerization and slurry polymerization. All state-of-the-art processes use either gas-phase or bulk reactor systems at 60 to 80° C.
  • the properties of polypropylene (0.895 and 0.92 g/cm 3 density) are strongly affected by its tacticity, the orientation of the methyl groups relative to the methyl groups in neighboring monomer units.
  • the tacticity of polypropylene (isotactic polypropylene, syndiotactic polypropylene, atactic polypropylene) can be chosen by the choice of an appropriate Ziegler- Natta or metallocene organometallic catalyst.
  • FIG. 1 shows a diagram of pyrolysis of waste plastics fuel or wax that is generally operated in the industry today.
  • polyethylene and polypropylene wastes are sorted together 1.
  • the cleaned polyethylene/polypropylene waste 2 is converted in a pyrolysis unit 3 to offgas 4 and pyrolysis oil (liquid product).
  • the offgas 4 from the pyrolysis unit is used as fuel to operate the pyrolysis unit.
  • a distillation unit in the pyrolysis unit separates the pyrolysis oil to produce naphtha and diesel 5 products which are sold to fuel markets.
  • the heavy pyrolysis oil fraction 6 is recycled back to the pyrolysis unit 3 to maximize the fuel yield.
  • Char 7 is removed from the pyrolysis unit 3.
  • the heavy fraction 6 is rich in long chain, linear hydrocarbons, and is very waxy (i.e., forms paraffinic wax upon cooling to ambient temperature). Wax can be separated from the heavy fraction 6 and sold to the wax markets.
  • the pyrolysis product treatment of the present process can be done efficiently in conjunction with the pyrolysis unit during the pyrolysis oil and wax manufacturing. Or the treatment can be done at the refinery before feeding the pyrolysis oil and wax to the refinery units.
  • the present fine filtration and metal oxide treatment process does not reduce S and N impurities, nor olefin and diene contents.
  • refinery units such as a fluid catalytic cracking (FCC) unit, a FCC feed pretreater, refinery crude unit, coker, distillate hydrotreater or hydrocracker.
  • FCC fluid catalytic cracking
  • the present process converts pyrolyzed polyethylene and/or polypropylene waste plastic in large quantities by integrating the waste polymer pyrolysis product streams into an oil refinery operation.
  • the resulting processes produce the feedstocks for the polymers (naphtha or C3-C4 or C3 only for a propylene polymerization unit), high quality gasoline, jet and diesel fuel, and/or quality base oil.
  • polypropylene is produced via polymerization of pure propylene.
  • a pyrolysis unit produces poor quality products containing contaminants, such as calcium, magnesium, chlorides, nitrogen, sulfur, phosphorus, silicon, dienes, and heavy components, which products cannot be used in large quantity for blending in transportation fuels. It has been discovered that by having these products go through the refinery units, the contaminants can be captured in pre-treating units and their negative impacts diminished.
  • the fuel components can be further upgraded with appropriate refinery units with chemical conversion processes, with the final transportation fuels produced by the integrated process being of higher quality and meeting the fuels quality requirements.
  • the present process will upgrade the wax into valuable gasoline, diesel and base oil.
  • the integrated process will generate a much cleaner C3 for propylene generation and polypropylene production.
  • FIG. 2 depicts a process sequence of a fine filtration and metal oxide treatment.
  • the cleaned polyethylene/polypropylene waste 22 is passed through a pyrolysis reactor 23 to thermally crack at least a portion of the polyolefin waste and produce a pyrolyzed effluent.
  • Char 26 is generally removed from the pyrolysis reactor 23.
  • the effluent is passed through a heat exchanger 60 for partial cooling and then to a gas-liquid separation unit 61.
  • Offgas 24 can be used as fuel to operate the pyrolysis unit.
  • the liquid product from the pyrolysis effluent is then passed to a fine filtration unit 27-1.
  • any pyrolysis wax produced can also be passed to the fine filtration (and metal oxide treatment).
  • the fine filtration unit removes solids in the pyrolysis oil, particularly chars created by the pyrolysis process and inorganic solids arising from contamination. Metals are often present as inorganic solids in the form of metal chlorides, metals or metal oxides. Thus, the fine filtration process reduces the contaminants coming from chars, metals, metal oxides, and metal chlorides.
  • a very fine filter medium needs to be used, preferentially less than 5 micron, more preferentially less than 2.5 micron and most preferentially less than 1 micron nominal-rated filter. Multiple filter units with different size filter elements may be used in series. These filter media are well known for industrial uses.
  • the filter media must be able to withstand the temperature of the pyrolysis oil as well as the chemical nature of especially the contaminants.
  • the residual solid content can be measured, for example, by Heptane Insolubles test, ASTM D- 3279 method.
  • the content of Heptane Insolubles needs to be reduced to less than 0.5 wt%, preferably less than 0.1%.
  • the chloride and impurity removal is more effective when the metal oxide treatment temperature is done above 200° F (93° C), preferentially above 300° F (149° C), and most preferentially above 400° F (204° C).
  • Preferred pressure range is from atmospheric pressure to 1000 psig, preferentially from 0 psig to 600 psig.
  • Fh gas may be added to the treating process.
  • the preferred amount of Fh gas flow is ranging from 0 to 2000 scf/bbl of pyrolysis oil.
  • Metal oxides with high surface area can also capture additional contaminants. Metal oxides such as Cao, ZnO, MgO, alumina, silica, clay and silica-alumina are effective for chloride removal.
  • Mixed metal oxides made of Mg, Ca, A1 or Zn, or combination of these are particularly effective for organic chloride removal. It is desirable to reduce the chloride content to less than 10 ppm, preferably less than 5 ppm and most preferably less than 1 ppm. Metal oxides made of Ni, Mo, phosphate, alumina, silica and silica-alumina or combination of these are particularly effective for residual metals removal while they can also remove other contaminants such as chlorides, nitrogen, phosphorus and silicon. It is desirable to reduce the total residual metals content to less than 10 ppm, preferably less than 5 ppm. Combination of different metal oxides can be used for effective removal of impurities.
  • the treated effluent can then be cooled in heat exchanger 62, with the entire treated, liquid product (naphtha, distillate and heavy fraction) 25 then passed on to refinery units 63.
  • the pyrolysis unit can be located near the waste plastics collection site, which site could be away from a refinery, near a refinery, or within a refinery. If the pyrolysis unit is located away from the refinery, then pyrolysis oil (naphtha/diesel and heavies) can be transferred to the refinery by truck, barge, rail car or pipeline. It is preferred, however, that the pyrolysis unit is within the waste plastics collection site or within the refinery.
  • a fine filtration and metal oxide treatment 27 is effected at the pyrolysis facility.
  • the whole liquid pyrolysis product 25 from the pyrolysis unit 23 is sent to the filtration unit followed by an oxide treatment. It is preferred that the hot pyrolysis liquid is filtered and treated with the metal oxide before it is completely cooled to ambient temperature for storage and/or transfer. Thus, it is preferred for the filtration and metal oxide treatment to occur at the pyrolysis facility after the whole liquid product 25 is recovered or to occur simultaneously with the whole liquid product collection step.
  • the treated liquid product can then be transferred to the refinery. In another embodiment, the whole liquid product 25 can be transferred to a refinery and the fine filtration and metal oxide treatment 27 is completed at the refinery.
  • the preferred starting material for the present process is sorted waste plastics containing predominantly polyethylene and polypropylene (plastics recycle classification types 2, 4, and 5).
  • the pre-sorted waste plastics are washed and shredded or pelleted to feed to a pyrolysis unit for thermal cracking.
  • FIG. 4 depicts the plastic type classification for waste plastics recycling.
  • Classification types 2, 4, and 5 are high density polyethylene, low density polyethylene and polypropylene, respectively. Any combination of the polyethylene and polypropylene waste plastics can be used.
  • at least some polyethylene waste plastic is preferred.
  • Plastics waste containing polyethylene terephthalate (plastics recycle classification type 1), polyvinyl chloride (plastics recycle classification type 3) and other polymers (plastics recycle classification type 7) need to be sorted out to less than 5%, preferably less than 1% and most preferably less than 0.1%.
  • the present process can tolerate a moderate amount of polystyrene (plastics recycle classification type 6).
  • Waste polystyrene needs to be sorted out to less than 30%, preferably less than 20% and most preferably less than 5%.
  • Non- metal contaminants include contaminants coming from the Periodic Table Group IV A, such as silica, contaminants from Group VA, such as phosphorus and nitrogen compounds, contaminants from Group VIA, such as sulfur compounds, and halide contaminants from Group VIIA, such as fluoride, chloride, and iodide.
  • the residual metals, non-metal contaminants, and halides need to be removed to less than 50 ppm, preferentially less than 30ppm and most preferentially to less than 5ppm.
  • the pyrolyzing is carried out by contacting a plastic material feedstock in a pyrolysis zone at pyrolysis conditions, where at least a portion of the feed(s) is cracked, thus forming a pyrolysis zone effluent comprising primarily 1 -olefins and n-paraffms.
  • Pyrolysis conditions include a temperature of from about 400° C. to about 700° C., preferably from about 450° C. to about 650° C.
  • Conventional pyrolysis technology teaches operating conditions of above- atmospheric pressures. See e.g., U.S. Pat. No. 4,642,401. Additionally, it has been discovered that by adjusting the pressure downward, the yield of a desired product can be controlled. See, e.g., U.S. Pat. No. 6,150,577. Accordingly, in some embodiments where such control is desired, the pyrolysis pressure is sub-atmospheric.
  • fine filtration is meant a filter having a pore size of 5.0 micron or less, preferably 1.0 micron or less, and in one embodiment about 0.5 micron.
  • the treatment thereby allows large amounts of the waste plastic pyrolysis liquid product to be passed through the refinery for a most effective recycling process.
  • FIG. 3 shows the present integrated process, waste plastics pyrolysis, the filtering and metal oxide treatment, and the integrating refinery operations with recycle for effective polypropylene production.
  • the same numbers in FIG. 2 and FIG. 3 refer to the same type of units and product streams.
  • the cleaned waste plastic 22 is converted in a pyrolysis unit 23 to offgas 24 and a pyrolysis oil (liquid product).
  • the offgas 24 from the pyrolysis unit can be used as fuel to operate the pyrolysis unit 23.
  • the pyrolysis oil, the entire liquid product 25, comprises the naphtha, diesel distillates and heavy fractions.
  • Char 26 is removed from the pyrolysis unit 23 after completion of the pyrolysis step.
  • the entire pyrolysis oil (naphtha, distillate and heavy fractions) 25 is passed through filtering and metal oxide treatment 27, and then sent to a fluid catalytic cracking (FCC) unit 28.
  • FCC fluid catalytic cracking
  • only a portion of pyrolysis oil (the distillate and heavy fractions only or the heavy fraction only) can be sent to the FCC unit.
  • the fluid catalytic cracking (FCC) process is widely used in the refining industry for conversion of atmospheric gas oil, vacuum gas oil, atmospheric residues and heavy stocks recovered from other refinery operations into high-octane gasoline, light fuel oil, heavy fuel oil, olefin-rich light gas (LPG) and coke.
  • FCC uses a high activity zeolite catalyst to crack the heavy hydrocarbon molecules at a 950-990° F (510-532° C) reactor temperature in a riser with a short contact time of a few minutes or less.
  • LPG streams containing olefins are commonly upgraded to make alkylate gasoline, or to be used in chemicals manufacturing.
  • a conventional FCC unit is used.
  • the refinery will generally have its own hydrocarbon feed from petroleum derived oil flowing through the refinery units.
  • the flow volume of pyrolysis oil generated from the pyrolysis of waste plastic to the refinery units can comprise any practical or accommodating volume % of the total flow to the refinery units.
  • the flow of the pyrolysis oil (and wax) generated from the waste plastic pyrolysis for practical reasons, can be up to about 50 vol.
  • the flow of the pyrolysis oil is an amount up to about 20 vol. % of the total flow. In another embodiment, the flow of the pyrolysis oil is an amount up to about 10 vol. % of the total flow. About 20 vol. % has been found to be an amount that is quite practical in its impact on the refinery while also providing excellent results and being an amount that can be accommodated. The amount of pyrolysis oil and wax generated from the pyrolysis can of course be controlled so that the fraction passed to the refinery units provide the desired volume % of the flow.
  • the LPG olefin stream 31 is a C3 liquid petroleum gas (LPG) fraction containing propane and propylene.
  • the C3 stream of propane and propylene mix is separated by a propane/propylene splitter (PP splitter) 34 to produce pure streams of propylene 35 and propane 36.
  • the propylene stream 35 can be fed directly to the polypropylene polymerization unit 40.
  • the pure propane may be fed to a propane dehydrogenation unit 37 to make propylene 35, and then ultimately polypropylene in a propylene polymerization unit 40.
  • Dehydrogenation of propane is practiced widely in the industry to produce propylene.
  • the reaction is endothermic, conversion is maintained by multi-stage reactors and inter-stage heaters.
  • the unit typically operates at high temperature (>900° F) and low pressure ( ⁇ 50 psig) in the presence of noble metal (Pt) catalyst.
  • Pt noble metal
  • the multi-stage process generates approximately 85% purity propylene/ propane mixture.
  • This stream is directed to a propane-propylene (P-P) splitter which is a high efficiency distillation column.
  • the splitter produces pure propylene stream with 99.5-99.8% purity.
  • the LPG olefin stream 32 is a C4 liquid petroleum gas (LPG) fraction containing butanes and butenes. This fraction may be sent to a refinery alkylation unit (not shown) or upgraded or blended into gasoline.
  • LPG liquid petroleum gas
  • the FCC gasoline 29 can be sent to a gasoline blending pool.
  • the heavy portion 30 recovered from the FCC unit 28 is sent to appropriate refinery units 38 (such as hydrotreating, hydrocracking and/or coker units) for upgrading into clean gasoline and diesel 39.
  • the C4 stream 32 is either sent to a gasoline blending pool or further upgraded (via processes such as alkylation or C4 olefin dimerization or ether synthesis) into clean gasoline.
  • the polypropylene polymer made in the propylene polymerization unit 40 can then be made into consumer products 41.
  • the propylene polymerization unit is preferably located near the refinery so that the feedstocks (propane and propylene) can be transferred via pipeline.
  • the feedstock can be delivered via truck, barge, rail car or pipeline.
  • the treated pyrolysis oil is first sent to an FCC feed pretreater (not shown) before the FCC unit.
  • the FCC feed pretreater typically uses a bimetallic (NiMo or C0M0) alumina catalyst in a fixed bed reactor to hydrogenate the feed with Fk gas flow at a 660- 780° F (349-415° C) reactor temperature and 1,000-2,000 psi (6.89-13.79 MPa) pressure.
  • the refinery FCC feed pretreater unit is effective in removing sulfur, nitrogen, phosphorus, silica, dienes and metals that will hurt the FCC unit catalyst performance. Also this unit hydrogenates aromatics and improves the liquid yield of the FCC unit.
  • the carbon in and out of the refinery operations are “transparent,” meaning that all the molecules from the waste plastic do not necessarily end up in the exact olefin product cycled back to the polyolefin plants, but are nevertheless assumed as “credit” as the net “green” carbon in and out of the refinery is positive. With these integrated processes, the amount of virgin feeds needed for polyethylene plants will be reduced substantially.
  • Example 1 Properties of Pyrolysis Oil and Wax From Commercial Sources
  • Pyrolysis oil and wax samples were obtained from commercial sources and their properties are summarized in Table 1. These pyrolysis samples were prepared from waste plastics containing mostly polyethylene and polypropylene via thermal decomposition in a pyrolysis reactor at around 400-600° C, near atmospheric pressure without any added gas or a catalyst.
  • a pyrolysis unit typically produces gas, liquid oil product, optionally wax product, and char.
  • the pyrolysis unit ’s overhead gas stream containing thermally cracked hydrocarbon was cooled to collect condensate as pyrolysis oil (liquid at ambient temperature) and/or pyrolysis wax (solid at ambient temperature).
  • the pyrolysis oil is the main product of the pyrolysis units. Some units produce pyrolysis wax as a separate product in addition to the pyrolysis oil.
  • ASTM D4052 method was used for specific gravity measurements. Simulated boiling point distribution curve was obtained using ASTM D2887 method. Carlo-Erba analysis for carbon and hydrogen was based on ASTM D5291 method. Bromine number measurement was based on ASTM D1159 method. Hydrocarbon-type analysis was done using a high resolution magnetic mass spectrometer using the magnet scanned from 40 to 500 Daltons. Total sulfur was determined using XRF per ASTM D2622 method. The nitrogen was determined using a modified ASTM D5762 method using chemiluminescence detection. The total chloride content was measured typically using combustion ion chromatography (CIC) instrument using modified ASTM 7359 method.
  • CIC combustion ion chromatography
  • the oxygen content in naphtha and distillate boiling range was estimated using GC by GC/MS measurements with electron ionization detector for m/Z range of 29-500. Trace metal and non-metal elements in oil were determined using inductively coupled plasma-atomic emission spectrometry (ICP-AES).
  • ICP-AES inductively coupled plasma-atomic emission spectrometry
  • Industrial pyrolysis process of sorted plastics sourced predominantly from polyethylene and polypropylene waste, produced quality hydrocarbon streams with specific gravity ranging 0.7 to 0.9, and a boiling range from 18 to 1100° F as in pyrolysis oil or pyrolysis wax.
  • the pyrolysis product is rather pure hydrocarbon made of mostly carbon and hydrogen.
  • the hydrogen to carbon molar ratio varies from 1.7 to near 2.0.
  • the Bromine Number is in the range of 14 through 60 indicating varying degrees of unsaturation coming from olefins and aromatics.
  • the aromatic content is in the range of 5 to 23 volume % with a higher severity unit producing more aromatics.
  • the pyrolysis products show paraffinic content ranging from mid-20 vol. % to mid-50 vol. %.
  • the pyrolysis product contains a substantial amount of olefins.
  • Samples A and B pyrolysis oil produced under more severe conditions such as higher pyrolysis temperature and/or longer residence time, contain higher aromatic and lower paraffinic components, resulting H/C molar ratio of around 1.7 and high Bromine Number of 50-60.
  • Samples C and D were produced at less severe conditions, and the pyrolysis oils are more paraffinic, resulting H/C molar ratio of close to 2.0 and Bromine Number around 40.
  • Sample E pyrolysis wax, is mostly paraffinic, saturated hydrocarbon with a substantial amount of normal hydrocarbons (as opposed to branched hydrocarbons) with low Bromine Number of only 14.
  • Example 2 Contaminants in Pyrolysis Oils and Micro Filtration to Remove Solids
  • Pyrolysis oils or wax products contain residual solids and other impurities that could negatively affect the performance of conversion units in a refinery. As received pyrolysis oil samples were vacuum filtered through 0.7 micron glass fiber filter paper to remove residual solids and the results are summarized in Table 2.
  • the residual solid content can be measured by the Heptane Insolubles test, ASTM D- 3279 method.
  • ASTM D- 3279 method For chloride analysis, X-ray fluorescence (XRF) method was used.
  • Example 2-5 The data suggests that a pyrolysis oil product contains varying amounts of inorganic chloride species and filtration can reduce the impurity level substantially. In Example 2-5, however, no reduction of chloride species was observed. This suggests that some chloride species are organic in nature and further treatment would be needed beyond the filtration process.
  • Example 3 Pyrolysis Oil Pretreating by Filtration followeded by CaO/ZnO/Clay Metal Oxide Treatment
  • Sample F-l was further treated by passing it through a fixed bed reactor containing metal oxide adsorbent made of CaO/ZnO/Clay.
  • the metal oxide treating experiments were carried out at 600 psig reactor pressure and 1 LHSV flow, with the temperature varying from 200 to 400° F. 1500 SCF/BBL of hydrogen was fed to the reactor with the oil. The results are summarized below in Table 4.
  • the metal oxide treatment step removed a substantial amount of metal (Fe) and other non-metals (N, Cl, P, Si) that could negatively affect the performance of conversion units in a refinery.
  • CaO and ZnO containing metal oxides were particularly effective for chloride and iron removal. The removal became more efficient at a higher temperature.
  • Example 4 Pyrolysis Oil Pretreating by Filtration followeded by NiO/MoOa/POi/Alumina Metal Oxide Treatment
  • Sample G-l was further treated by passing it through a fixed bed reactor containing metal oxide adsorbent made of NiO/MoCb/PC Alumina.
  • the metal oxide treating experiments were carried out at 400 psig reactor pressure and 1 LHSV flow, with the temperature varying from 500 to 550 °F. 1500 SCF/BBL of hydrogen was fed to the reactor with the oil. The results are summarized below in Table 6.
  • the metal oxide treatment step removed a substantial amount of metals (Fe, Ca, Cr, Mg) and other non-metals (N, Cl, P, Si) that could negatively affect the performance of conversion units in a refinery. M0O3 and NiO containing metal oxides were particularly effective for metals removal at about 500-550° F.
  • the following Examples 5 through 8 show the evaluation of waste plastics pyrolysis oil for transportation fuel.
  • Example 5 Fractionation of Pyrolysis Oil for Evaluation As Transportation Fuel [0075] Sample D was distilled to produce hydrocarbon cuts representing gasoline (350° F ), jet (350 - 572° F), diesel (572 - 700° F) and the heavy (700° F + ) fractions. Table 7 summarizes the boiling point distribution and impurity distributions among the distilled product fractions.
  • Example 6 Evaluation of Pyrolysis Oil Cut for Gasoline Fuel
  • Sample H a pyrolysis oil cut for gasoline fuel boiling range, was evaluated to assess its potential for use as a gasoline fuel. Sample H has the carbon number range of C5 - C12, typical of a gasoline fuel.
  • Sample H a pyrolysis oil cut for gasoline fuel boiling range, cannot be used by itself as automotive gasoline fuel due to its poor quality.
  • the gasoline fraction from the pyrolysis oil showed very poor oxidation stability in that Sample H failed only after 90 min compared to the target stability of longer than 1440 minutes.
  • the pyrolysis gasoline exceeded the wash gum target of 4 mg/ 100 mL suggesting severe gum forming tendency.
  • the pyrolysis gasoline has poor octane numbers compared to the reference gasoline. A premium unleaded gasoline was used as the reference gasoline.
  • Example 7 Evaluation of Pyrolysis Oil Cut for Jet Fuel
  • Sample I a pyrolysis oil cut for jet fuel boiling range, was evaluated to assess its potential for use as jet fuel. Sample I has the carbon number range of C9 - C18, typical of the jet fuel.
  • Example 8 Evaluation of Pyrolysis Oil Cut for Diesel Fuel
  • Sample J a pyrolysis oil cut for diesel fuel boiling range, was evaluated to assess its potential for use as diesel fuel. Sample J has the carbon number range of C14 - C24, typical of a diesel fuel.
  • Sample J contains a substantial amount of normal hydrocarbons. Since normal hydrocarbons tend to exhibit waxy characteristics, cold flow properties such as pour point (ASTM D5950-14) and cloud points (ASTM D5773) were considered as the most critical tests. [0090] Two blends were prepared at 10 and 20 volume % of Sample J with refinery produced diesel fuel. However, both blends still failed the target pour point of less than -17.8° C (0° F) pour points.
  • Example 9 Coprocessing of Pyrolysis Product to FCC Unit
  • the pyrolysis oil and wax are converted into offgas, LPG paraffins and olefins, FCC gasoline and heavy hydrocarbon components.
  • the FCC gasoline is a valuable gasoline blending component.
  • the heavy fractions, light cycle oil (LCO) and heavy cycle oil (HCO) are converted further in the subsequent conversion units including jet hydrotreating unit, diesel hydrotreating unit, hydrocracking unit and/or coker unit to make more gasoline, jet, and diesel fuel with satisfactory product properties.
  • LPG paraffins and olefins can be either processed further in an alkylation unit or in part used for petrochemicals production with a recycle content.
  • Example 10 Conversion of Pyrolysis Oil in FCC
  • VGO Vacuum gas oil
  • the FCC experiments were carried out on a Model C ACE (advanced cracking evaluation) unit fabricated by Kayser Technology Inc. using regenerated equilibrium catalyst (Ecat) from a refinery.
  • the reactor was a fixed fluidized reactor using N2 as a fluidization gas.
  • Catalytic cracking experiments were carried out at the atmospheric pressure and 900° F reactor temperature. The cat/oil ratio was varied between 5 to 8 by varying the amount of the catalyst.
  • a gas product was collected and analyzed using a refinery gas analyzer (RGA), equipped with GC with FID detector. In-situ regeneration of a spent catalyst was carried out in the presence of air at 1300° F, and the regeneration flue gas was passed through a LECO unit to determine the coke yield.
  • RAA refinery gas analyzer
  • the FCC unit cracks the pyrolysis oil info fuel range hydrocarbons, reduces impurities, and isomerize n-paraffins to isoparaffins. All these chemistry will improve the fuel properties of the pyrolysis oil and wax.
  • a zeolite catalyst By cofeeding the pyrolysis oil through the FCC process unit with a zeolite catalyst, the oxygen and nitrogen impurities in the fuel range were reduced substantially, from about 300-1400 ppmN to about 30 ppmN and from about 250-540 ppm O to about 60-80 ppm O.
  • the hydrocarbon composition of all these cofeeding products are well within the typical FCC gasoline range.
  • Example 11 Coprocessing of Pyrolysis Wax in a FCC
  • Sample E and VGO To study the impact of coprocessing of waste plastics pyrolysis wax in a FCC, a series of laboratory tests were carried out with Sample E and VGO. FCC performances of 20% blend of pyrolysis wax with VGO and pure pyrolysis wax were compared with that of the pure VGO feed, similar to Example 10. The results are summarized below in Table 12.
  • Example 12 Feeding of Recycled C3 for Propylene Isolation or Production, followeded by Productions of Polypropylene Resin and Polypropylene Consumer Products
  • the pyrolysis product cofeeding to a FCC unit, as shown in Examples 10 and 11 produces a substantial amount of C3 LPG steam with a recycle content.
  • the C3 stream is a good feedstock to feed to a polymerization unit for production of polypropylene polymer with a recycle content.
  • the C3 LPG steam containing propane and propylene is captured and fed to a propane/propylene (P/P) splitter to isolate a pure propylene steam (>99 mol%), which is then fed to a propylene polymerization unit.
  • the propane from the P/P splitter may be dehydrogenated to produce additional propylene for the polymerization unit.
  • the polypropylene resin containing some recycled-polyethylene/ polypropylene derived materials is of high quality and is indistinguishable from that of a virgin polypropylene resin made entirely from virgin petroleum resources.
  • the polypropylene resin with the recycled material can then be further processed to produce various polypropylene products to fit the needs of consumer products.
  • These polypropylene consumer products now contain chemically recycled, circular polymer while qualities of the polypropylene consumer products are indistinguishable from those made entirely from virgin polypropylene polymer.
  • These chemically recycled polymer products are different from the mechanically recycled polymer products whose qualities are inferior to the polymer products made from virgin polymers.
  • Example 13 Quality Gasoline, Jet and Diesel Product Production with Recycle Content
  • Cofeeding of pyrolysis oil and/or wax to a FCC unit produces a substantial amount of C3 - C5 olefins with a recycle content, as well as the gasoline, jet, diesel products.
  • the C4 only or C4 - C5 stream containing recycled olefins is separated from FCC light-end recovery units, and then fed to an alkylation unit.
  • Reaction of LPG olefins and isobutane in the alkylation reactor produces n-butane and alkylate gasoline with recycle contents.
  • Alkylate gasoline and n-butane are valuable gasoline blending components.
  • the heavy fraction is further upgraded in a hydrocracking unit to produce quality gasoline, jet and diesel products.
  • the word “comprises” or “comprising” is intended as an open-ended transition meaning the inclusion of the named elements, but not necessarily excluding other unnamed elements.
  • the phrase “consists essentially of’ or “consisting essentially of’ is intended to mean the exclusion of other elements of any essential significance to the composition.
  • the phrase “consisting of’ or “consists of’ is intended as a transition meaning the exclusion of all but the recited elements with the exception of only minor traces of impurities.

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Abstract

Un mode de réalisation de la présente invention concerne un procédé continu permettant de convertir des déchets plastiques comprenant du polyéthylène et/ou du polypropylène en produit de recyclage pour la polymérisation de polypropylène. Le procédé consiste à sélectionner des déchets plastiques contenant du polyéthylène, du polypropylène ou un mélange de ceux-ci et à faire passer les déchets plastiques dans un réacteur de pyrolyse pour craquer thermiquement au moins une partie des déchets de polyoléfine et produire un effluent pyrolysé. L'effluent pyrolysé est séparé en un gaz de dégagement, une huile de pyrolyse comprenant des fractions naphta, diesel et des fractions lourdes, et un produit de carbonisation. L'huile de pyrolyse, ou au moins une fraction est amenée à subir un traitement de filtration/par oxyde métallique, le produit traité étant introduit dans une unité FCC de raffinerie. Une fraction de mélange oléfine en C3/paraffine de gaz de pétrole liquéfié est récupérée à partir de l'unité FCC, ainsi qu'une fraction de mélange oléfine en C4/paraffine. La fraction d'oléfine en C3 peut être transmise à un réacteur de polymérisation de propylène, et la paraffine en C3 transmise à une unité de déshydrogénation pour produire du propylène en vue d'une polymérisation supplémentaire.
EP21793603.8A 2020-04-22 2021-04-22 Économie circulaire de déchets plastiques en polypropylène par raffinage d'huile avec filtration et traitement d'oxyde métallique d'huile de pyrolyse Pending EP4139420A4 (fr)

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US20210332300A1 (en) 2021-10-28
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JP2023522976A (ja) 2023-06-01
JP7692932B2 (ja) 2025-06-16
KR20230004715A (ko) 2023-01-06
CA3177035A1 (fr) 2021-10-28
WO2021216873A1 (fr) 2021-10-28
MX2022012742A (es) 2022-11-07
US11359147B2 (en) 2022-06-14
EP4139420A4 (fr) 2024-05-29

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